Hydrochloric Acid → [11-(Acryloyloxy)undecyl]phosphonic acid

HRID 1952421Notes

Reaction equation

HRID 1952421 reaction equation
[C:1]([O:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][P:17]([O:22]CC)([O:19]CC)=[O:18])(=[O:4])[CH:2]=[CH2:3].[Si](Br)(C)(C)C.Cl>C(Cl)Cl>[C:1]([O:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][P:17](=[O:18])([OH:22])[OH:19])(=[O:4])[CH:2]=[CH2:3]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 76113BromotrimethylsilaneHCID 5917200411-(Diethoxyphosphoryl)undecyl prop-2-enoate

Product 1

HCID 59172001[11-(Acryloyloxy)undecyl]phosphonic acidYield 40.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

11-(diethoxyphosphoryl)undecyl acrylate (420 mg, 1.16 mmol) was dissolved in ˜5 mL dry DCM. TMS bromide (0.33 mL, 2.55 mmol) was added via syringe and the rbf was greased and capped and allowed to stir for 2 hours. The solvent was concentrated by rotary evaporation and the product mixture redissolved in ˜3 mL methanol and ˜5 mL water and stirred for 2.5 hours during which a white precipitate formed. 1 M HCl was added and the product was extracted into dichloromethane, dried over magnesium sulfate, and pumped dry. The yellow/brown solid was dissolved in hot acetonitrile and put in the freezer overnight. Filtration afforded a white solid (143 mg, 40% yield). 1H NMR (300 MHz, CDCl3) δ 9.82 (br, s, 2H), 6.40 (dd, J=17.32, 1.61 Hz), 6.12 (dd, J=17.32, 10.41 Hz), 5.81 (dd, J=10.40, 1.60 Hz), 4.15 (t, J=6.73 Hz, 2H), 1.82-1.50 (m, 6H), 1.42-1.18 (m, 14H). 13C{1H} NMR (125.77 MHz, CDCl3) δ 166.76, 130.85, 129.05, 65.12, 30.87 (d, J=17.38 Hz), 29.89, 29.88, 29.76, 29.65, 29.46, 29.01, 26.33, 25.76 (d, J=143.86 Hz), 22.45 (d, J=4.85 Hz). Analysis found (calculated) %: C, 55.09 (54.89); H, 8.79 (8.88). 31P{1H}NMR (161.97 MHz, CDCl3): δ 38.76.

Workup

  1. customcapped
  2. concentrationThe solvent was concentrated by rotary evaporation
  3. dissolutionthe product mixture redissolved in ˜3 mL methanol
  4. stirring˜5 mL water and stirred for 2.5 hours during which a white precipitate
  5. customformed
  6. extractionthe product was extracted into dichloromethane
  7. dry with materialdried over magnesium sulfate
  8. custompumped dry
  9. dissolutionThe yellow/brown solid was dissolved in hot acetonitrile
  10. customput in the freezer overnight
  11. filtrationFiltration

Sources & evidence

ORD record
ord-30b9305d90bc4e1798d9b0aeeece9af2
Source dataset
uspto-grants-2013_03
Patent number
US08405069B2

Reaction notes

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